Low emissions one part adhesive

ABSTRACT

An adhesive composition which can be formulated to have low or substantially no VOC emissions is provided. Adhesives in accordance with the invention can be formulated as high solids, one-part, reactive, cross-linked adhesives. This can be achieved by utilizing amide-ester-acrylate reactions or reactions with any other carboxylated polymers. Adhesive compositions in accordance with the invention can include oils, such as various drying oils and similarly acting polymers, co-polymers, and fatty acids. Adhesives in accordance with the invention can also include various hydrocarbon resins, particularly crosslinkable hydrocarbons having a melting point in the range 70° C. to 140° C. Cross-linking agents, such as materials with pendant oxazoline groups are also advantageously included. Various other mixing, flow and other handling ingredients can also be included.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to provisional application No.60/284,954, filed on Apr. 19, 2001 the contents of which areincorporated herein by reference.

FIELD OF THE INVENTION

The invention is directed to a low emissions one part adhesives andmethods of making the same.

BACKGROUND OF INVENTION

The invention relates generally to adhesives, such as flooringadhesives, and more particularly, to adhesives that have low emissionsof undesirable materials, such as volatile organic compounds (VOCs).

Many products are assembled using adhesives. For example, variousflooring products made from wood, vinyl, tile, carpet and so forth arepermanently adhered to a surface or substrate through the use of anadhesive. Commonly used adhesives include those sold under thetrademarks Taylor Enviotec 2090 Vinyl Adhesive and Taylor Envirotec 2055Premium Carpet Adhesive sold, by W. F. Taylor Co. of Fontana, Calif.

There are at least two general types of adhesives: two componentadhesives and one component adhesives. Two components reactive adhesivesare generally formed with a resin component and a hardener component andthe resin and hardener are mixed immediately prior to application. Thiscauses a chemical reaction to occur which typically initiates some typeof cross-linking process. Two component adhesives are often consideredundesirable because considerable mixing of the components must occurjust prior to use. This can be inconvenient. Also, just the right amountof adhesive must be mixed prior to application. If too much is mixed, orthe working “pot” time is exceeded, the adhesive will harden and theexcess must be discarded. Reactive urethane type adhesives containmaterials such as isocyanates, which are often considered undesirable.

Single component adhesives can be more convenient to use than twocomponent adhesives. Many single component adhesives are solvent-basedadhesives in which an adhesive composition is mixed with a solvent andpackaged in a drum, can or tube. After the adhesive is applied to asubstrate, the solvent evaporates, which causes the adhesive to cure.

The solvents used in certain conventional solvent-based adhesives arebelieved by some to be undesirable. For example, many solvent-basedadhesives emit VOCs. Depending on the working environment, availableventilation, and the amount of adhesive to be used, some consider theVOC's and other emitted chemicals to be disadvantageous. Other singlecomponent adhesives contain excessive amounts of water, which can damagewood surfaces. There are other single component reactive adhesives suchas moisture cure urethanes, but they typically exhibit emission problemsbecause they give off solvents and other potentially dangerous materialssuch as isocyantes (MDI and TDI).

Accordingly, it is desirable to provide an improved adhesive whichovercomes drawbacks and inadequacies of conventional adhesives.

SUMMARY OF THE INVENTION

Generally speaking, in accordance with the invention, a one componenthigh strength adhesive composition which can be formulated to have lowor substantially no VOC emissions is provided. Adhesives in accordancewith the invention can be formulated as high solids, one-part, reactive,cross-linked adhesives. This can be achieved by utilizingamide-ester-acrylate reactions or reactions with any other carboxylatedpolymers. Adhesive compositions in accordance with the invention caninclude oils, such as various drying oils and similarly acting polymers,co-polymers, and fatty acids. Metal naphthanates can be used to catalyzethe drying speed when the adhesive composition is applied to asubstrate.

Adhesives in accordance with the invention can also include varioushydrocarbon resins, particularly crosslinkable hydrocarbons having amelting point in the range 70° C. to 140° C. These can be dissolved orotherwise mixed in the drying oil component. For example, C-5hydrocarbon resins formed from hydrocarbons having an average of aboutfive carbon atoms and C-9 hydrocarbon resins formed of hydrocarbonshaving an average of about 9 carbon atoms and preferably both, mixed ineffective proportions to provide desired cured strength, green strength,open working times and so forth can be satisfactory.

Adhesives in accordance with the invention can also include fugitivealkali agents, such as ammonia, monomethanol amine (MEA) and triethanolamine (TEA). Cross linking agents, such as materials with pendantoxazoline groups, such as latex polymer solutions and emulsions whichinclude those groups are also advantageously included. Various othermixing, flow and other handling ingredients can also be included.

High solids construction adhesives in accordance with the invention canbe particularly useful in assembling various flooring products made fromwood, vinyl, ceramic, rubber to various substrates common to flooringinstallations including: concrete, plywood, underlayment grade particleboard, vinyl, ceramic tile, cement patches and underlayments, radiantheat flooring and terrazzo. Adhesives in accordance with the inventioncan benefit from polymer emulsions with carboxyl functionality, polymeremulsion cross-linkers containing pendant oxazoline group are alsoadvantageously employed. Other useful ingredients include tackifyinghydrocarbon resins dissolved in drying oils; napthanates of metals suchas cobalt, calcium, zirconium, and manganese; fugitive bases for pHadjustment; and other stabilizing agents, such as fugitiveanti-oxidants.

Accordingly, it is an object of the invention to provide an improvedadhesive.

Another object of the invention is to provide an improved method ofmaking an adhesive.

Still other objects of the invention will in part be obvious and will,in part, be apparent from the specification. The invention accordinglycomprises the composition of matter, the method of making a compositionof matter and the method of using the composition of matter which willbe exemplified in the compositions and methods hereinafter described,and the scope of the invention will be indicated in the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

In the drawing figures, which are merely illustrative:

FIG. 1 is a graph depicting shear strength development over three monthsaging, comparing the performance of a preferred embodiment of theinvention with a leading moisture cure urethane adhesive on the market.As demonstrated in FIG. 1, an adhesive in accordance with the preferredembodiments of the invention is immediately stronger than a leadingmoisture cure urethane adhesive, cures to have higher shear strength anddoes not give off unacceptable VOCs while curing; and

FIG. 2 is a graph showing increase in cross link density of an adhesiveformulated in accordance with a preferred embodiment of the invention,with progressing time.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention is directed to adhesive compositions and methods of makingadhesive compositions which can include ingredients set forth below. Theinvention also relates to methods of applying flooring involving the useof those adhesives. As will be evident to those of ordinary skill in theart, substitutions, omissions and additions will be possible in order toprovide adhesives with customized selected properties.

Preferred ingredients, preferred percentages of components and mixingprocesses in accordance with preferred embodiments of the invention willbe set forth below in Table 1.

TABLE 1 Preferred Amount Preferred Ingredient wt % Preferred Process 1Drying Oils such as Linseed  4 to 10 Oil, Tung Oil, Sunflower Oil,Cashew Shell Oil, Castor Oil, Coconut Oil, Cotton Seed Oil, Fish Oil,Oiticica Oil, Rapeseed Oil, Safflower Oil, Sesame Oil, Soybean Oil,Walnut Oil, Synthetic Drying Oils, Tall Oil, Fatty Acids, or any blendof the above. 2 Aliphatic C-5 Hydrocarbon  4 to 10 Resin with asoftening point of between about 75° and 115° C., such as that producedfrom Acyclic Aliphatic monomers such as Cis 1,3 Pentadiene, Trans 1,3Pentadiene, 2- Methyl 2 Butene, Dicyclopentadiene Copolymers,Vinyltoluene Copolymers 3 Alkylated Aromatic C-9 Resin 10 to 20Ingredient 2 and 3 are combined with a softening point of withIngredient 1. Temperatures of between about 100° and between about 240°and 30° F. may 140° C., produced from C-8 to be required to form asubstantially C-10 monomers such as homogenous solution. This Styrene,Vinyl Toluene, homogenous solution should be Indene, Methyl Indene,Alpha held at between about 250° and Methyl Styrene. 260° before beingcombined with the ingredients below. 4 Surfactants, such as 6 to 10 0.50to 1.50 Add ingredients 4 and 5 to mole ethoxylates of ingredient 6while mixing until nonylphenols and other uniform. emulsifying agentssuch as saponified esters. 5 Anti-foaming agents such as 0.05 to 0.10non-silicon anti-foaming agents 6 Polymer emulsions or hot melt 30 to 60Maintain the temperature of polymers (advantageously high ingredient 6to between 60° and 90° solids) with carboxyl F. Add ingredients 4 and 5while functionality, such as Acrylic, mixing until uniform. Then add theStyrene Butadiene, EVA, VAE premixed ingredients 1, 2 and 3 above toingredient 6 with high shear agitation until ingredients form ahomogenous emulsion. 7 Fugitive anti-oxidants such as 0.10 to 1.00 Addwhile agitating oximes such as methyl ethyl ketoxime, Bactericide,Fungicides, and Freeze-Thaw Stabilizers 8 Fugitive alkali agent, such as0.10 to 1.00 Use the alkali to adjust the above Ammonia, MEA, TEAemulsion pH to between 8-10 before adding ingredients 9 and 10 9Dispersing Agent, such as salts 0.10 to 1.00 Add while agitating of polyacrylic acid 10 Napthanates of metals such as 0.10 to 1.00 Add whileagitating cobalt, calcium, zirconium, and manganese 11 Polymer emulsionwith 1.00 to 7.00 Add while agitating pendant oxazaoline groups 12Fillers such as Calcium 20 to 40 Add slowly with high shear Carbonate,Kaolin Clay, Mica, agitation Talc, Silica, etc.

Adhesive compositions in accordance with the invention advantageouslyinclude liquids that can be used to dissolve and blend otheringredients, but which can be easily and readily oxidized and/orpolymerized to transform into a hard, dry material after exposure toair. Examples of such material include relatively highly unsaturatedoils and polymers, such as those identified above as drying oils. Thedrying oil component can be included as about 1 to 20%, preferably 4 to10%, more preferably about 2% to 5%. By dissolving (mixing) the resinsin the drying oil component and the addition of fugitive anti-oxidants,the resins can be prevented from cross-linking until the drying oil isexposed to air and hardens. The cross-linking starts as the compositionstarts to dry and the fugitive anti-oxidant starts to evaporate. Thus,there should be sufficient anti-oxidant to prevent the composition fromcuring too quickly, and to provide sufficient open time and ease ofhandling. Preferred open time should be up to about 30 and sometimes upto about 60 minutes and depend on the desired application.

Adhesives in accordance with the invention can also include hydrocarbonresins. The resins are selected to give the cured adhesive the desiredamount of cured strength. Appropriate selection of resins also affectsthe uncured strength (initial shear strength) of the adhesive, oftenreferred to as green strength. For example, if the adhesive is used as aflooring adhesive, it is desirable that the uncured adhesive maintainthe applied flooring in place with reasonable security so that tiles,for example, can be aligned properly and so that minor bumps and nudgesdo not require reseating and realignment of the flooring materials.Below is a comparison of typical green strength in psi, of adhesives inaccordance with a preferred embodiment of the invention compared to aleading VOC emitting Moisture Cure Urethane Adhesive currently on themarket:

Cure Time 15 Min 30 Min 45 Min 60 Min 3 Hour 6 Hour 16 Hour 24 HourInvention Adhesive 5 22 23 32 45 50 86 94 Moisture Cure Urethane 1 1 1 17 28 53 57

Cure Time 1 week 1 month 2 months 3 months Invention Adhesive 158 269325 448 Moisture Cure Urethane 100 132 153 174

Conventional moisture Cure Urethane adhesives can contains up to 1%4,4′-Diphenylmethane Diisocyanate (MDI), up to 1% Toluene Diisocyante,up to 10% Aliphatic Petroleum Distillates, up to 1% Ethyl Benzene, Up to5% Xylene, Up to 7% Mineral Spirits and up to 1.5% 1,2,4-TrimethylBenzene. All these VOCs are listed in the hazardous materials section ofthe MSDS for most commercial grade moisture cure urethane adhesives.

It has been determined that the cured strength and green strength of theadhesive can be related to the softening points of the resin material.As used herein, softening point will refer to the temperature at whichviscous flow of a material that does not have a definite melting pointchanges to plastic flow.

Resins in accordance with preferred embodiments of the inventiongenerally have softening points between 75° C. and 140° C. It has alsobeen determined that by mixing resins with different softening points,advantageous characteristics of each resin can be realized. For example,resins with a relatively low softening point, e.g., about 95-105° C.will have up to 30-40% less green strength and cured strength thanresins with a relatively high softening point in the range of e.g.,115-130° C. Softening point also affects processing and handlingproperties. If a softening point is too high, desired materials might bedifficult to emulsify at temperatures needed for proper mixing.

In one embodiment of the invention, a resin formed with hydrocarbonshaving, on average, 6 or fewer carbon atoms and a softening pointpreferably between 75° C. and 115° C. is combined with a relativelyharder resin formed from hydrocarbons having an average of 7 or morecarbon atoms and a softening point preferably about between 100° C. and140° C.

In preferred embodiments of the invention, the relatively soft resin isan aliphatic hydrocarbon resin formed of hydrocarbons having an averageof about 5 carbon atoms. Advantageous resins can be formed from acyclicaliphatic monomers, such as cis 1, 3 pentadiene, trans 1, 3 pentadiene,and 2-methyl 2 butene and cyclopentadienes.

Adhesive compositions in accordance with the invention alsoadvantageously include a relatively harder hydrocarbon resin,particularly one having a higher temperature softening point in therange of 100° C. to 140° C. In particular, alkylated aromatic resins,particularly those formed from hydrocarbons having an average of 8 to 10carbon atoms, such as those produced from C-8, C-9 and C-10 monomers,such as styrene, vinyl toluene, indene, methyl indene, alpha methylstyrene. Particularly suitable C-9 resins include petroleum aromatichydrocarbon resins having softening points in the range 100° C. to 135°C. These relatively harder resins are advantageously included as 10 to20%, preferably 12% to 18%. Other non-limiting examples of suitable C-9and C-5 Resins are described below in Table 2. Adhesives in accordancewith the invention can also be formulated with Versadil 100, Versadil101 and Versadil 200.

TABLE 2 Manufacturer C-9 Resins C-5 Resins Rutgers VFT AG Novares TT120Varziner Strasse 49, D-47138 Novares TT130 Duisburg Germany SartomerCompany Norsolene S115, Oaklands Corporate Center Norsolene S125, 502Thomas Jones Way Norsolene S135 Exton, PA 19341 Exxon Chemicals Escorez1102 Houston Escorez 1304 2401 S. Gessner Escorez 1310LC Houston, TX77063-2005, USA Escorez 1315 Escorez 1580 Neville Chemical CompanyNevchem 110 Lx-1200 2800 Neville Road Nevchem 120 Lx-1200-130Pittsburgh, PA 15225 Nevchem 130 Lx-2600-125 Nevex 100 Eastman ChemicalCompany Petrorez 100 P.O. Box 431 Kingsport, TN 37662 Petrorez 199Petrorez 200 Resinall Resinall 711 Resinall 769 3065 High Ridge RoadResinall 717 P.O. Box 8149 Resinall 736 Stamford CT 06903 Resinall 737Resinall 747 Resinall 771 Resinall 774 TOSOH Corporation Petcoal ® 100Suite 600, 1100 Circle Petcoal ® 120 75 Parkway, Atlanta, GA Petcoal ®120HV 30339-3097, Petcoal ® 140 U.S.A. Arakawa CHEMICAL (USA) INC. ArkonSM-10 625 N. Michigan Avenue - Suite #1700 Arkon SP10 Chicago, IL 60611USA Grenhall Chemicals Limited Resin GC100, 7686 Bath Road, Resin GC300,Mississauga, ON Canada L4T 1L2 Resin GC400 Hercules Inc. Picco 5120Piccotac 115 Resins Division Picco 6115 Piccotac B Hercules Plaza 1313North Market Street Wilmington, DE 19894 Yuen Liang Industrial Co., LtdPetroresin (yl-series, sk-series, qs- South Korea series b-series withsoftening point of between 90-130° C. Sunbelt Chemicals, Inc. SB1000R100AS 407 N. Cedar Ridge, Suite 230 SB1100 S105A Duncanville, Texas75116 SB140ES R100G LUKOIL Bulgaria PYROLEN 100 Bulgaira 1421 Sofia, 59A Cherni Vrah Blvd

When preparing adhesive compositions in accordance with the invention,the low softening point resins (with 6 or fewer carbon atoms) areadvantageously provided in the drying oil component in about a 2:1 to1:2, preferably 1:1 weight ratio. The mixture of ingredients 1 and 2 ofTable 1 can then be advantageously heated to a temperature above thesoftening point of the high temperature resin, preferably in the rangeof 115° C. to 140° C. with mixing, to form a generally homogeneouscombination. Care should be taken to insure that the composition is notheated to a temperature too far over the softening points of thematerials or it can be difficult to blend with the rest of theingredients. Thus, after a homogeneous combination is achieved, thetemperature can be reduced to a point when ease of mixing is maintained,generally approximately 115° C. to 130° C.

Surfactants, such as 6 to 10 mole ethoxylates of nonylphenols can beincluded, advantageously in the range of less than 5% by weight,advantageously 0.5 to 1.5%.

It is also advantageous to include anti-foaming agents, in particular,non-silicon anti-foaming agents. These are advantageously included asless than about 0.5 weight percent, preferably 0.05 to 0.10 weightpercent.

Adhesives in accordance with the invention also advantageously includepolymer emulsion materials, particularly those having carboxylfunctionality to provide enhanced adhesive properties, such as thosehaving acrylic, styrene butadiene, ethylene vinyl acetate copolymer(EVA) and vinyl acetate ethylene copolymer can be included as about 20to 80%, preferably about 30 to 60%, more preferably about 35 to 55% ofthe composition. The emulsion should be maintained at a temperature ofabout 15 to 30° C. Ingredients 4 and 5 can then be added and mixed untiluniform. Ingredients 1, 2 and 3 are then added with high shear agitationuntil the ingredients form a substantially homogeneous blend.

Compositions in accordance with the invention also advantageouslyinclude fugitive anti-oxidants, such as oximes, such as methyl ethylketoxime, bactericides, fungicides and freeze/thaws stabilizers.

Compositions in accordance with the invention also advantageouslyinclude fugitive alkali agents, such as ammonia, monomethanol amine(MEA) and triethanolamine (TEA). This alkali agent can be useful toadjust the pH of the emulsion to at least 7, preferably between about 8and 10 before the oxazoline containing component is added.

Adhesive compositions in accordance with the invention can also includeup to 2%, preferably 2.1 to 1% dispersing agents, such as salts ofpolyacrylic acids and dryers, in particular naphthanates of metals, suchas cobalt, calcium, zirconium and manganese. The dryers should beincluded in an effective amount to catalyze the drying speed of thedrying oil to a desired rate. The precise amount will depend on both thedesired speed of cure and the particular composition of the adhesive.These should be added with agitation.

Adhesive compositions in accordance with the invention alsoadvantageously include oxazole containing materials, in particular,polymer emulsion materials that include pendant oxazoline groups. Thereshould preferably be about a 1:1 mole ratio between carboxly groups inthe composition and oxazoline groups. If too much of these materials areadded, it will lower the possible solids content. If too little is addedthere will be lower cross link density and a weaker adhesive.

Oxazolines are 5-membered heterocyclic compounds, having the generalformula C₃H₃NO and are frequently used in organic synthesis. Emulsionscontaining particles of an oxazoline-modified polymer containing pendantoxazoline groups are discussed in U.S. Pat. Nos. 4,474,923, 4,508,869and 4,325,856, the contents of which are incorporated herein byreference. Preferred oxazolines have the following formula:

wherein R¹ is an acyclic or organic radical having additionpolymerizable unsaturation; each R² is independently hydrogen, halogenor an inertly substituted, organic radical and n is 1 or 2. Theoxazoline containing emulsion preferably also includes at least oneother addition polymerizable monomer which is copolymerizable with theoxazoline and discrete particles of a coreactive polymer whichcoreactive polymer had been prepared in an emulsion polymerizationprocess from (1) an addition, polymerizable coreactive monomercontaining pendant groups which are capable of reacting with anoxazoline group to form covalent bonds thereto and (2) at least oneother monomer which is copolymerizable with said coreactive monomer.

Adhesive compositions in accordance with the invention can also includeeffective amounts of fillers, such as calcium carbonate, kaolin clay,mica powder, talc and so forth. Fillers should generally represent lessthan 50% of the composition, preferable in the range of 20-40% of thecomposition. If too much filler is included the cohesive strength of theproduct can be reduced. If too little filler is included, the solidscontent will be too low for many applications.

These components should be added slowly, with high shear agitation, toensure a substantially homogeneous mixture.

After adhesive compositions in accordance with the invention aredeposited, the polymer emulsion containing the oxazoline groups isbelieved to become available to act as a cross-linking agent to cure thecarboxylated polymers. Accordingly, a one component self-curing adhesivewhich can be made substantially or entirely free of VOC's can beachieved.

In another non-limiting embodiment of the invention, the process bywhich the adhesive in accordance with the invention is made can be splitinto two stages. The first stage can comprise the blending of the firstseven ingredients and storing, with constant slow agitation, theresulting mixture as a premix to be used the final blend. The secondstage comprises blending the last five ingredients with the premix.

Prior to blending the premix with the remaining ingredients, the premixmay be cooled to a temperature preferable in the range of 75° F. to 110°F. The cooling may occur using such devices as: a cooling jacket withcold water, a cooling jacket with a cooling tower, heat exchanger, aflash vacuum cooling system, or any other cooling device that can lowerthe temperature to within the desired range. Heat exchangers such asshell and tube heat exchangers, spiral heat exchangers, plate and frameheat exchangers, or compabloc welded plate heat exchangers may be used.

After blending the premix with the remaining ingredients and prior topackaging the composition, the final temperature of the batch should becooled to a temperature of preferably not more than 90° F.

Areas designed to house electrical equipment or various manufacturing ortesting procedures often need to avoid the build-up of staticelectricity. In another non-limiting embodiment of the invention,adhesives in accordance with the invention can be rendered electricallyconductive. Conductive adhesive are advantageously used in constructingElectrostatic Dissipative Floors (ESD) by the inclusion ofelectro-conductive agents in the adhesive composition. Particularlysuitable electro-conductive agents include carbon black, syntheticconductive fibers, electrically conductive metal chips or fragments, orany other conductive materials such as conductive nano materials.

Table 3, below provides formulation information for preparingelectrically conductive adhesives in accordance with the invention.Table 3 also shows an alternative manufacturing process, which can alsobe used with the non-conductive adhesive. Other processing steps can besubstituted such as those in Table 1.

TABLE 3 Conductive Adhesive Preferred Preferred Ingredients Amount wt %Preferred Process 1 Drying Oil such as Linseed oil,  4 to 10 Tung Oil,Sunflower Oil, Cashew Shell Oil, Castor Oil, Coconut Oil, Cotton SeedOil, Fatty Acids, Fish Oil, Oiticica Oil, Rapeseed Oil, Safflower Oil,Sesame Oil, Soybean Oil, Walnut Oil, Synthetic Drying Oils, Tall Oil,Fatty Acids, 2 Aliphatic C-5 Hydrocarbon Resin 4 to 10 with a softeningpoint of between 75° and 115° C., such as those produced from AcyclicAliphatic monomers such as Cis 1,3 Pentadiene, Trans 1,3 Pentadiene,2-Methyl 2 Butene, Dicyclopentadiene Copolymers, VinyltolueneCopolymers, 3 Alkylated Aromatic C-9 Resin 10 to 20 Ingredient 2 and 3are dissolved with a softening point of between in ingredients 1 attemperatures about 100° and 140° C., produced of between 240° and 300°F. to from C8 to C-10 monomers such form a homogenous solution. asStyrene, Vinyl Toluene, Indene, This homogenous solution Methyl Indene,Alpha Methyl should be held at between 250° Styrene. and 260° F. beforebeing added to ingredients below. 4 Surfactants, such as 6 to 10 mole0.50 to 1.50 Ingredients 1 through 5 should ethoxylates of nonylphenols.be premixed and then heated 5 Anti-foaming agents, such as Non- 0.05 to0.10 and maintained at temperature Silicon Anti-foaming agents betweenabout 240° and 260° F. 6 Polymer emulsion, advantageously 30 to 60Pre-heat and maintain the with high solids content, e.g. Latextemperature of ingredient 6 to Polymer with Carboxyl between 60° and100° F. Add Functionality, such as Acrylic, the premixed ingredientsabove Styrene Butadiene, EVA, VAE. to ingredient 6 with high shearagitation until ingredients form a homogenous emulsion. 7 Fugitiveanti-oxidants, Bactericide, 0.10 to 1.00 Add while agitating Fungicides,and Freeze-Thaw Stabilizers Stage one is the blending of the first 7ingredients and storing preferably (with constant slow agitation). Theresulting mixture is used as a premix to be used in the final blend.Prior to blending the premix above with the rest of the ingredientsbelow, the premix should be coded. 8 Dispersing Agent, such as salts of0.10 to 1.00 Add while agitating poly acrylic acid. 9 Electro-conductiveagents such as; 5.0 to 15.0 Add while agitating Carbon black, SyntheticConductive Fibers, Electrically Conductive metal chips or fragments, orany other conductive materials such as Conductive Nano Materials 10Napthanates of metals such as 0.10 to 1.00 Add while agitating cobalt,calcium, zirconium, and manganese 11 Fugitive alkali agent, such as 0.10to 1.00 Use the alkali to adjust the Ammonia, MEA, TEA above emulsion pHto between 8-10 before adding ingredients 9 and 10 12 Fillers such asCalcium carbonate, 20 to 40 Add slowly with high shear Kaolin Clay,Mica, Talc etc agitation 13 Latex polymer emulsion with 1.00 to 7.00 Addwhile agitating pendant oxazoline groups The final temperature of thebatch should be cooled to a temperature of not more than 90° F., priorto packaging.

The following examples are provided for purposes of illustration onlyand should not be construed as limiting the scope of the invention.

TABLE 4 Shear Strength Data (psi) at various Cure Times 15 Min 30 Min 45Min 1 Hour 3 Hour 6 Hour 16 Hour 24 Hour Example 1 4.3 11.6 26.2 29.845.3 50.3 86.6 94.0 Example 2 4.1 20.7 23.3 29.4 38.9 43.2 81.5 89.1Example 3 4.9 21.7 23.3 31.5 45.3 50.3 85.7 94.0 Conventional 1 1 1 1 728 53 57 Moisture Cure Urethane

As shown in Table 4, the adhesive of Examples 1-3, set forth below,exhibited excellent green strength and cure strength compared toconventional adhesives such as moisture cure urethane and exhibitedacceptably low VOC emissions while curing.

Table 5, below, provides non-limiting examples of application examples.As shown, adhesive in accordance with the invention can be used to applya wide variety of flooring. Acceptable coverage depends on theunderlying floor substrate and the backing of the flooring to beapplied. However, coverage in the range of about 20 to 300 ft²/galloncan be acceptable, preferably about 20-150 ft²/gallon for wood; 100-300ft²/gallon for vinyl or ceramic and 50-150 ft²/gallon for carpet. Theadhesive can be applied using any suitable dispensing method such astrowelling, spray pumping, extrusion and so forth.

TABLE 5 Application Devices and Application Rates Installation TrowelSize Coverage Application (width × depth × spacing) (square feet pergallon) Carpet or {fraction (3/32)}″ × {fraction (3/32)}″ × {fraction(3/32)}″ v notch 100-120 Wood Carpet ⅛″ × ⅛″ × {fraction (1/16)}″ vnotch  75-108 Carpet ⅛″ × ⅛″ × {fraction (1/16)}″ u notch 36-63 Vinyl{fraction (1/16)}″ × {fraction (1/16)}″ × {fraction (1/16)}″ sq. notch150-180 Vinyl {fraction (1/16)}″ × {fraction (1/32)}″ × {fraction(1/32)}″ u notch 180-250 Wood ⅛″ × ⅛″ × ⅛″ sq. notch 60-80 Wood{fraction (3/16)}″ × {fraction (3/16)}″ × {fraction (3/16)}″ sq. notch30-40 Wood {fraction (3/16)}″ × ¼″ × ½″ V notch 50-60

Example 1 - Construction Adhesive Ingredient Amount wt % Process 1Linseed Oil 6.00 2 Aliphatic C-5 6.00 Hydrocarbon Resin with a softeningpoint of 85° C. 3 Alkylated Aromatic 14.25 Ingredient 2 and 3 aredissolved in C-9 Resin with a ingredients 1 at temperatures of softeningpoint of between 240° and 300° F. to form a 115° C. homogenous solution.This homogenous solution should be held at between 250° and 260° F.before being added to ingredients below. 4 9 mole ethoxylates 1.00 Addingredients 4 and 5 to of nonylphenols ingredient 6 while mixing untilsurfactant uniform. 5 Non-Silicon Anti- 0.25 foaming agent 6Carboxylated High 43.00 Maintain the temperature of Solids Acrylicingredient 6 to between 60° and 90° F. Add ingredients 4 and 5 whilemixing until uniform. Then add the premixed ingredients 1, 2, and 3above to ingredient 6 with high shear agitation until ingredients form ahomogenous emu 7 Fugitive anti- 0.05 Add while agitating oxidant, andFreeze-Thaw Stabilizer 7 Bactericide, and 0.05 Add while agitatingFungicides 8 Ammonia 0.50 Use the alkali to adjust the above emulsion pHto between 8-10 before adding ingredients 9 and 10 9 Dispersing Agent,0.20 Add while agitating such as salts of poly acrylic acid. 10 Cobalt,0.20 Add while agitating Managanese, and Manganese Napthanates 11Polymer emulsion 1.50 Add while agitating with pendant oxazoline groups12 Calcium Carbonate 27.00 Add slowly with high shear agitation

Example 2 Construction Adhesives Ingredient Amount wt % Process 1 TungOil 6.00 2 Aliphatic C-5 6.00 Hydrocarbon Resin with a softening pointof 85° C. 3 Alkylated Aromatic C-9 14.25 Ingredient 2 and 3 aredissolved Resin with a in ingredients 1 at temperatures softening pointof 115° of between 240° and 300° F. to C. form a homogenous solution.This homogenous solution should be held at between 250° and 260° F.before being added to ingredients below. 4 9 mole ethoxylates of 1.00Add ingredients 4 and 5 to nonylphenols surfactant ingredient 6 whilemixing until uniform. 5 Non-Silicon Anti- 0.25 foaming agent 6Carboxylated High 43.00 Maintain the temperature of Solids Styreneingredient 6 to between 60° and Butadiene Rubber 90° F. Add ingredients4 and 5 while mixing until uniform. Then add the premixed ingredients 1,2, and 3 above to ingredient 6 with high shear agitation untilingredients form a homogenous emu 7 Fugitive anti-oxidant, 0.05 Addwhile agitating and Freeze-Thaw Stabilizer 7 Bactericide, and 0.05 Addwhile agitating Fungicides 8 Ammonia 0.50 Use the alkali to adjust theabove emulsion pH to between 8-10 before adding ingredients 9 and 10 9Dispersing Agent, such 0.20 Add while agitating as salts of poly acrylicacid. 10 Cobalt, Managanese, 0.20 Add while agitating and ManganeseNapthanates 11 Polymer emulsion with 1.50 Add while agitating pendantoxazoline groups 12 Calcium Carbonate 27.00 Add slowly with high shearagitation

Example 3 - Construction Adhesive Ingredient Amount wt % Process 1Sunflower Oil 6.00 2 Aliphatic C-5 Hydrocarbon Resin 6.00 with asoftening point of 85° C. 3 Alkylated Aromatic C-9 Resin 14.25Ingredient 2 and 3 are with a softening point of 115° C. dissolved iningredients 1 at temperatures of between 240° and 300° F. to form ahomogenous solution. This homogenous solution should be held at between250° and 260° F. before being added to ingredients below. 4 9 moleethoxylates of 1.00 Add ingredients 4 and 5 to nonylphenols surfactantingredient 6 while mixing until uniform. 5 Non-Silicon Anti-foamingagent 0.25 6 Carboxylated High Solids Styrene 43.00 Maintain thetemperature of Butadiene Rubber ingredient 6 to between 60° and 90° F.Add ingredients 4 and 5 while mixing until uniform. Then add thepremixed ingredients 1, 2, and 3 above to ingredient 6 with high shearagitation until ingredients form a homogenous emu 7 Fugitiveanti-oxidant, and Freeze- 0.05 Add while agitating Thaw Stabilizer 8Bactericide, and Fungicides 0.05 Add while agitating 9 Ammonia 0.50 Usethe alkali to adjust the above emulsion pH to between 8-10 before addingingredients 9 and 10 10 Dispersing Agent, such as salts of 0.20 Addwhile agitating poly acrylic acid. 11 Cobalt, Managanese, and 0.20 Addwhile agitating Manganese Napthanates 12 Polymer emulsion with pendant1.50 Add while agitating oxazoline groups 13 Kaolin Clay 7.00 Add slowlywith high shear agitation 14 Calcium Carbonate 20.00 Add slowly withhigh shear agitation

Table 6 below provides Moisture Transmission Data (per ASTM 96-00) ofadhesive in accordance with a preferred embodiment of the inventionversus leading Moisture Cure Urethane Wood Adhesive which emitundesirable VOCs.

TABLE 6 ASTM 96-00 Moisture Transmission, Adhesive G/m2(24 hr-mm Hg) Apreferred embodiment 0.59. of the invention Commercial Moisture Cure1.20. Urethane Wood Adhesive 1 Commercial Moisture Cure 0.60. UrethaneWood Adhesive 2

Low moisture transmission permits an adhesive to act as a moisturebarrier. Table 6 shows that adhesives in accordance with the inventioncan be formulated to have at least as good moisture barrier propertiesas conventional urethane adhesives, but without the same level of VOCemissions.

FIG. 1 shows that in certain respects, adhesives in accordance with theinvention can have enhanced adhesive properties compared withconventional urethane adhesives. Adhesives in accordance with theinvention can be formulated to have a shear strength of over 5 psi, evenover 10 psi at 15 minutes, and over 10 psi, even over 20 psi at 30 min.Final cure strengths (at 3 months) can exceed 200 psi, and can evenexceed 300 psi or 400 psi. The adhesive used for FIG. 1 exhibited ashear strength of 450 psi. In addition to exhibiting advantageous greenstrengths, adhesives in accordance with the invention also exhibitdesirable open times. Even at open times of up to 60 minutes theadhesive will still exhibit advantageous strength characteristics.

FIG. 2 shows the progression of cross-link density with time for oneembodiment of the invention. Adhesives in accordance with the inventioncan be formulated to exhibit an immediate initiation of cross-linkingand a steady progression for the first hour. Different embodiments ofthe invention can be formulated to exhibit faster or slowerprogressions, varying by e.g.—about 10 or 20%, or otherwise depending onthe desired applications.

It will thus be seen that the objects set forth above, among those madeapparent from the preceding description, are efficiently attained, and,since certain changes may be made in carrying out the above method andin the compositions set forth without departing from the spirit andscope of the invention, it is intended that all matter contained in theabove description and shown in the accompanying drawings shall beinterpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended tocover all of the generic and specific features of the invention hereindescribed and all statements of the scope of the invention which, as amatter of language, might be said to fall therebetween.

Particularly it is to be understood that in said claims, ingredients orcompounds recited in the singular are intended to include compatiblemixtures of such ingredients wherever the sense permits.

What is claimed is:
 1. An adhesive composition, comprising: thecombination produced by combining effective amounts and proportions of adrying oil component; a hydrocarbon resin component; a fugitive alkaliagent component; a fugitive anti-oxidant component; a dryer component;and a cross linking agent with pendant oxazoline groups component, toprovide an adhesive that can be applied to a substrate and which willcure on the substrate.
 2. The adhesive composition of claim 1, whereinthe resin component comprises a C-5 hydrocarbon component and a C-9hydrocarbon component.
 3. The adhesive composition of claim 1, whereinthe hydrocarbon resin component comprises a hydrocarbon resin having asoftening point from about 70° C. to 140° C.
 4. The adhesive compositionof claim 1, wherein the drying oil component comprises at least onemember selected from the group consisting of linseed oil, tung oil andsunflower oil.
 5. The adhesive composition of claim 1, wherein thedrying oil component comprises at least one member selected from thegroup consisting of cashew shell oil, castor oil, coconut oil, cottonseed oil, fish oil, oiticica oil, rapeseed oil, safflower oil, sesameoil, soybean oil, walnut oil, tall oil, and fatty acids.
 6. The adhesivecomposition of claim 2, wherein the C-5 hydrocarbon has a softeningpoint from between 75° C. to 115° C.
 7. The adhesive composition ofclaim 2, wherein the C-5 hydrocarbon is selected from the groupconsisting of cis 1,3 pentadiene, trans 1,3 pentadiene, and 2-methyl 2butene.
 8. The adhesive composition of claim 2, wherein the C-9hydrocarbon has a softening point from between 100° C. to 140° C.
 9. Theadhesive composition of claim 2, wherein the C-9 hydrocarbon is selectedfrom the group consisting of styrene, vinyl toluene, indene, methylindene, and alpha methyl styrene.
 10. The adhesive composition of claim1, wherein the fugitive alkali agent comprises a member selected fromthe group consisting of ammonia, monoethanol amine, and triethanolamine.
 11. The adhesive composition of claim 1, wherein the fugitiveanti-oxidant component comprises an oxime.
 12. The adhesive compositionof claim 1, wherein the pendant oxazoline group comprises latex polymeremulsions.
 13. The adhesive composition of claim 1, wherein the dryercomponent comprises a metal napthanate.
 14. The adhesive of claim 1, andcomprising a polymer emulsion component with carboxyl functionality. 15.The adhesive of claim 14, wherein the polymer emulsion componentcomprises acrylic, styrene, butadiene, EVA and/or VAE materials.
 16. Theadhesive of claim 13, wherein the metal is selected from the groupconsisting of cobalt, calcium zirconium and manganese.
 17. The adhesiveof claim 1, comprising an effective amount of electro-conductivematerial to render the cured adhesive electrically conductive.
 18. Theadhesive of claim 1, wherein the adhesive is formulated to substantiallylack VOCs that are emitted during curing.
 19. The adhesive of claim 1,wherein the drying oil component makes up about 1-20% of thecomposition.
 20. The adhesive of claim 1, wherein the hydrocarbon resincomponent comprises resins with 6 or fewer carbon atoms, at a ratio tothe drying oil component of about 2:1 to 1:2.
 21. The adhesive of claim1, wherein the adhesive has a formulation to cure to have a shearstrength of over 5 psi after 15 minutes.
 22. The adhesive of claim 1,wherein the adhesive has a formulation to cure to have a shear strengthof over 200 psi after 3 months.
 23. The adhesive of claim 1, wherein theadhesive has a formulation to exhibit an open time of up to 60 minutes.